Dyeing and printing fibers of natural and synthetic polyamides



United States Patent 3,442,600 DYEING AND PRINTING FIBERS OF NATURAL ANDSYNTHETIC POLYAMIDES Manfred Daeuble, Frankenthal, Pfalz, and KlausDieck, Hans Heinrich, Heinz-Guenther Witsch, and Dietmar Theilig,Ludwigshafen (Rhine), Germany, asslgnors to Badische Anilin- &Soda-Fabrik Aktiengesellschaft, Ludwigshafen am Rhine, Germany NoDrawing. Filed Mar. 10, 1966, Ser. No. 533,243 Claims priority,application Germany, Mar. 18, 1965,

Int. Cl. D06p /02, 3/24, 1/68 US. Cl. 8-54 8 Claims The presentinvention relates to a process for dyeing and printing fibers of naturaland synthetic polyamides with anionic dyes.

It is known that fibers of natural or synthetic polyamides (hereinaftercalled polyamide fibers), particularly those of wool, can be dyed orprinted by applying to material containing these fibers an aqueoussolution of an anionic dye at a temperature below that at which the dyewill go onto the fibers and then finishing off the dyeing or print bysteaming and/or introducing it into a hot acid liquor. This method hasserious disadvantages; for example it gives uneven dyeings.

It has therefore already been proposed to add further assistants to thedye solutions. In one known method of this type, condensation productsof high molecular weight fatty acids with two equivalents of analkanolamine, anion-active dispersing agents and if desired swellingagents for the fibers to be dyed are added as assistants to the dyesolution. Another prior proposal is to add a soluble salt of asaturated, aliphatic, high molecular weight monocarboxylic acid to thedye solution. These prior art methods have the disadvantage that theyrequire alkaline dye solutions because the assistants lose their effectin the acid range. Heat treatment of wool which has been impregnatedwith an alkaline liquor may however result in serious damage to thefibers.

It has therefore already been recommended that, to avoid thisdisadvantage, polyethylene glycol derivatives which have a chain of upto five ethylene oxide units attached at one end to a hydrophobicradical and at the other end to an anionic hydrophilic atom groupingshould be added as assistants to the dye solutions. It has been foundthat this method does not yield results which are to some extentsatisfactory unless the dye solution also contains a thickener. Themethod is therefore not universally applicable.

It is an object of the present invention to dye polyamide fibersuniformly by impregnation or printing with anionic dyes followed bysteaming and/or introduction into a hot acid liquor.

Another object of the invention is to achieve uniform dyeings and printsby such a method in continuous operation.

Yet another object of the invention is to dye or print woolen fiberswithout damage.

It is moreover an object of the invention to dye or print polyamidefibers without the coemployment of thickeners.

Finally it is an object of the invention to prevent the marked soilingof the apparatus used for dyeing and printing polyamide fibers.

These and other objects are achieved by the present invention.

We have found that the abovementioned disadvantages are avoided andpolyamide fibers can be dyed and printed particularly advantageously byapplying an aqueous solution which contains (a) at least one anionic dyeand (b) at least one anion-active assistant to the fibers at atemperature which is lower than the absorption temperature of all thedyes present and finishing off the dyeing or the print by steaming and/or introduction into a hot acid liquid (i.e. fixing the dye), when thesaid aqueous dye solution also contains (0) at least one adduct of 2 to8, preferably 3 to 6, moles of ethylene oxide to 1 mole of a linear orpreferably branched primary, secondary or tertiary alcohol having six toeighteen, preferably six to fifteen, carbon atoms or an adduct of 2 to6, preferably 2 to 4, moles of ethylene oxide to 1 mole of analkylphenol having six to fifteen carbon atoms in the alkyl radical and(d) at least one adduct of 1 to 2 moles of ethylene oxide to 1 mole of ahydroxy compound of the benzene or naphthalene series which may? bearfurther low molecular weight nonionic radicals on the aromatic nucleus.

The anionic dyes to be used according to this invention may belong toany class of dyes, such as the azo, anthraquinone, phthalocyanine ornitro dyes. They may be for example 1:1 or 1:2 metal-complex dyes freefrom or containing sulfonic groups, chrome dyes which may be usedtogether with agents yielding chromium, such as potassium dichromate,chromium fluoride or chromium acetate, or reactive dyes.

'Anionic dyes in the present specification are defined as dyes which aredescribed in the Colour Index (Second edition, 1956) as Acid Dyes,Mordant Dyes and Reactive Dyes.

Anion-active assistants are commonly used as additives in dyeing withanionic dyes. Preferred agents of this type are water-soluble salts ofsulfonic acids or sulfuric acid hemiesters which contain a hydrophobicgrouping in the molecule, especially their salts with alkali metals,ammonium and particularly organic bases. The following may be given asexamples: the water-soluble salts of sulfuric acid hemiesters ofaliphatic alcohols having ten to twenty, preferably twelve to eighteen,carbon atoms, of sulfuric acid hemiesters of adducts of alkylphenols and1 to 5 moles of ethylene oxide having six to twelve carbon atoms in thealkyl radical, of alkyl and alkylaryl sulfonic acids having ten totwenty carbon atoms and of N-acyltaurines having ten to twenty carbonatoms in the acyl radical. Further anion-active assistants are thewater-soluble salts of aminobenzenesulfonic acids which bear hydrophobicradicals as substituents on the nitrogen, and of sulfosuccinic alkylesters. It has proved to be particularly suitable to use at least 5parts by weight of anion-active assistant (b) to each 1000 parts byweight of dye liquor or print paste. In other respects it isadvantageous to adapt the amount of anion-active assistant to the amountof agent (c). If the latter is easily soluble in water or easilydispersable therein, a weight ratio of agent (b) to agent (c) of 0.25:1to 05:1 is sufiicient. On the other hand, if sparingly soluble andpoorly dispersable agents (c) are used, the said ratio is advantageouslyincreased, the upper limit being about 2:1. It is in fact possible toraise the amount of anionic agent even further but it is recommended, inthe interests of economical operation not to use more than 60 parts byweight of agent (b) to 1000 parts by weight of liquor or paste.

Starting materials for products of the type specified under (c) may bealkylphenols, preferably p-alkylphenols, which contain a linear orbranched alkyl radical having six to fifteen, preferably eight to ten,carbon atoms; they may also bear on the benzene nucleus low molecularweight alkyl radicals, such as methyl, ethyl, and propyl radicals, butmonoalkyl phenols are preferred. Other starting materials are linear orbranched aliphatic alcohols which contain six to eighteen, preferablysix to fifteen, carbon atoms. Examples of these are: p-n-hexylphenol,p-n-octylphenol, p-i-nonylphenol, o-n-decylphenol, m-ndodecylphenol,n-hexanol, 2-ethylhexanol, isooctanol,

nonanols, decanols, dodecanols, hexadecanols and octadecanols. Mixturesof such starting materials such as are obtained by syntheses or byderivation from natural raw materials, are also suitable. Branched-chainalcohols, such as are obtainable for example from oligomers of propyleneor butylene, such as trimeric propylene, tetrameric propylene,diisobutylene or triisobutylene, by oxo synthesis and hydrogenation, areparticularly advantageous as start ing materials.

The products defined under (c) are obtainable from these initialmaterials by adding on ethylene oxide in the amounts given above to thealkylphenols or alcohols by a conventional method.

It is however also possible for example to react alkylphenols withpreformed polyglycols and 2,2'-dichlorodiethyl ether in the presence ofsodium hydroxide to obtain products of the type defined under (c).

The agent (c) is used preferably in an amount of to 30 parts by weightto each 1000 parts by weight of dye liquor or print paste. Largeramounts may be used, but the economy of the process may suffer.

The adducts specified under (d) and derived from 1 to 2 moles ofethylene oxide and 1 mole of a hydroxy compound of the benzene ornaphthalene series are monophenyl ethers or mononaphthyl ethers ofethylene glycol or diethylene glycol. They may bear as further lowmolecular weight nonionic radicals, particularly halogen atoms,preferably chlorine atoms, hydroxyl groups, low molecular weight arylgroups, in particular phenyl groups, alkyl groups having up to fivecarbon atoms and/or alkoxy groups having up to five carbon atoms, on thearomatic nucleus. Examples are the reaction products of 1 to 2 moles ofethylene oxide with 1 mole of hydroxybenzene, 1-hydroxy-2-methylbenzene,1-hydroxy-4-methylbenzene, 1 hydroxy 4 phenylbenzene,1-hydroxy-2-methoxybenzene, l-hydroxynaphthalene, 2-hydroxynaphthalene,1,2- dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene and1,S-dihydroxynaphthalene. It is particularly advantageous to use theadduct of 1 mole of ethylene oxide to l-hydroxy-Z-chlorobenzene and tol-hydroxy-4- chlorobenzene.

The component (d) may be added to the liquor or paste preferably in anamount of 5 to 40 parts by weight with reference to 1000 parts by weightof liquor or paste. Whereas the efficacy of the agent gradually subsidesbelow the preferred range, it is not deleterious to use larger amounts.The limits are determined by economic considerations.

The liquor or paste may also contain the conventional additives, as forexample acids, such as acetic acid, swelling agents, such as benzylalcohol, solubilizers, such as low molecular weight alcohols, glycolsand butyrolactone, antifoaming agents, such as high molecular weightaliphatic alcohols, and thickeners. It is preferable, however, to useliquors which do not contain a thickener. When dyeing with dyes whichare capable of reacting with suitable metals with the formation ofcomplexes, for example the so-called chrome dyes, the mixture ofassistants may be salted out by the addition of the agents supplyingmetal, for example chromium fluoride or chromium acetate; this causesseparation into two layers and ineffectiveness of the system. This canbe prevented by adding chelate-forming agents, as for examplea-cyanocyclopentanone, p-diketo compounds or p-keto esters, such asacetylacetone, a-acetylbutrolactone, pentanone-Z-carboxylic esters oracetoacetic esters. The complex-forming metal is thus bound and losesthe property of salting out the assistant system from the solution. Itis not necessary to bind the metal ions completely, but about 1 mole ofthe chelating agent to 1 mole of the metal salt used, for examplechromium fluoride, is sufficient. It should however be taken intoconsideration that hydrogen ions are liberated by the chelate formationand contribute to the acidity of the liquor. Less acid is thereforerequired.

The salting-out action of the agents supplying metal on the assistantmixture may surprisingly also be suppressed 4 by using the dye, which isto react with the metal to form the complex, in dispersed form, theusual dye dispersing agents, such as alkali metal salts ofligninsulfonic acids or naphthalenesulfonic acid-formaldehyde reactionproducts, being coemployed. The fact that finely divided dyes may beused brings with it the further advantage that even in the case ofsparingly soluble chrome dyes, a colloidal solution may be obtained byscattering into warm water and this, after adding the assistantsaccording to this invention and chromium salts, may be used immediately,whereas when dyes which are not finely divided are used, the suspensionhas to be boiled before the assistants and chromium salts are added andthe remaining additives cannot be added until cooling has taken place.

Application of the dye liquor to the material to be dyed may be carriedout by printing, coating or spraying. It is preferable, however, to usethe padding method. Among the printing methods, the vigoureux printingof tops has proved to be especially suitable.

The temperature is kept below that at which all the dyes present wouldbe absorbed. The absorption temperature is that at which the dyemigrates from the aqueous dye solution to the material being dyed to anappreciable extent within the usual times of treatment; as used in thespecification, the term absorption temperature means the temperature atwhich half of the dye originally present in the dye solution willmigrate onto the material to be dyed within half an hour. It isadvantageous to bring the dye liquor onto the material to be dyed at atemperature which is as much as possible below the absorptiontemperature; it has proved to be particularly suitable to usetemperatures in the neighborhood of room temperature, i.e. at about 10to 40 C.

Fixing of the dye may be carried out in the conventional way bytreatment with steam at about to C. Another known measure for fixing thedye is treatment in a hot acid liquor. It is advantageous to introducethe material impregnated with the dye liquor into the acid liquor at atemperature of 80 to 98 C. It has proved to be particularly suitable tosubject the material to be dyed first to a short steam treatment inorder that the dye may be partly fixed and then to complete fixation ofthe dye in the hot acid liquor. Acids which are suitable for the acidliquor are inorganic and organic acids and also acid salts, examplesbeing sulfuric acid, phosphoric acid, hydrochloric acid, formic acid,acetic acid, sodium hydrogen sulfate, potassium hydrogen sulfate andammonium chloride. The acids or acid salts are advantageously used insuch an amount that the acid liquor has a pH value of 3 to 4. Organicacids are preferred, particularly formic acid. In some cases it isuseful to add water-soluble salts, preferably calcium salts, to the acidliquor.

After the dye has been fixed, the material may be washed, rinsed anddried in the usual way.

The process according to this invention may be carried out batchwise orcontinuously.

As compared with the prior art methods described earlier in thisspecification, the process aucording to the invention is distinguishedby the fact that the steps of the process can be varied to a greatextent; moreover the possibility of working in the absence of thickenersis particularly valuable. Thickeners may soil the apparatus used, forexample the steamer, to such a degree that when the dye is changed it isnecessary to carry out a cleaning of the apparatus lasting severalhours. When the present process has been used without thickeners, asimple spraying out of the apparatus with water is suflicient to cleanit.

Examples of polyamide fibers which may be dyed or printed according tothe invention are wool and other animal hair, silk, protein fibers andsynthetic polyamide fibers, such as those from e-caprolactam, fromadipic acid and hexamethylene diamine and from w-aminoundecanic acid.They may be dyed or printed according to the invention alone as mixtureswith each other or as mixtures with other fibers.

The present process is very well suited for dyeing tufted carpets ofsynthetic polyamide fibers. Whereas it has not been possible by priorart methods to dye these carpets continuously in a satisfactory manner,this is possible without difficulty by the process according to thisinvention; satisfactory dyeings are obtained even with 1:2 metalcomplexdyes, which tend to give very streaky dyeings on tufted goods.

For dyeing and printing synthetic polyamide fibers it has proved to beparticularly suitable to add to the dyeing or printing mixtures, adductsof more than moles,'preferably up to 80 moles, of ethylene oxide to 1mole of an oxalkylatable compound containing a hydrophobic grouping inthe molecule. Oxalkylatable compounds suitable as starting materials forthese adducts are particularly aliphatic alcohols having ten to twentycarbon atoms, alkylphenols having ten to twenty carbon atoms,saturatedand unsaturated fatty acids having ten to twenty carbon atoms,their glycerides and their reaction products with alkanolamines andprimary and secondary alkylamines having ten to twenty carbon atoms.Examples of such adducts are: the adduct of 40 moles of ethylene oxideto 1 mole of castor oil or to 1 mole of the reaction product of a fattyacid, such as oleic acid or stearic acid, with diethanolamine. Additionof 2 to 4 parts by weight of these products to 1000 parts by weight ofan impregnating liquor is usually sufiicient.

The invention is illustrated by the following examples. The parts areparts by weight.

EXAMPLE 1 30 parts of finely divided dye C.I. No. 15,675 is dissolved in500 parts of water, then 20 parts of the triethanolamine salt ofp-n-decylbenzenesulfonic acid, parts of the adduct of 6 moles ofethylene oxide to 1 mole of isodecanol, 10 parts of p-chlorophenylmonoethylene glycol ether (i.e. the adduct of 1 mole of ethylene'oxideto 1 mole of 1 hydroxy-4-chlorobenzene) and 15 parts of glacial aceticacid are added and the whole is made up to 1000 parts with water.

This padding liquor is used to impregnate wool tops at a temperature of30 to 35 C.; the tops are then squeezed out to a liquor retention ofabout 110%. The material is then steamed at 100 to 102 C. with saturatedsteam for fifteen minutes and then washed in warm water at about 40 to45 C.

A deep bluish red dyeing is obtained which does not exhibit any greystreaks.

An equally good result is obtained when the wool tops, afterimpregnation and squeezing out, are treated for only ten minutes withsaturated steam at 100 to 102 C., then brought into a boiling bathcontaining 5 g./l. of formic acid and having a pH value of 3.5 for fiveminutes and then washed.

A similar result is obtained when the adduct of 6 moles of ethyleneoxide to 1 mole of isodecanol is replaced by an equal amount of anadduct of 3 moles of ethylene oxide to 1 mole of n-hexanol, or of 6moles of ethylene oxide to 1 mole of pentadecanol or of 8 moles ofethylene oxide to 1 mole of n-octadecanol.

EXAMPLE 2 35 parts of the finely divided dye C.I, No. 15,710 isdissolved in 600 parts of water and then parts of the diethanolaminesalt of p-n-dodecylbenzene sulfonic acid, 20 parts of the adduct of 4moles of ethylene oxide to 1 mole of isononanol, 10 parts ofp-chlorophenyl monoethylene glycol ether, parts of chromium fluoride and20 parts of glacial acetic acid are added and the whole is made up to1000 parts with water.

Wool tops are impregnated with this padding liquor, squeezed out andsteamed in an atmosphere of saturated steam for forty-five minutes at100 to 102 C. After the dyed material has been washed with water, ablack dyeing is obtained which is fast to rubbing and exhibits nostreaks.

Deep black dyeings which are fast to rubbing are similarly obtained byusing the following compounds instead of the adduct of 4 moles ofethylene oxide to 1 mole of isononanoli (a) 15 parts of an adduct of 2moles of ethylene oxide to 1 mole of p-isononylphenol;

(b) 20 parts of the adduct of 6 moles of ethylene oxide to 1 mole ofisodecanol;

(c) 20 parts of the adduct of 6 moles of ethylene oxide to 1 mole ofisotridecanol;

(d) 15 parts of the adduct of 4 moles of ethylene oxide to 1 mole ofisooctanol;

(e) 25 parts of the adduct of 3 moles of ethylene oxide to 1 mole ofp-n-hexylphenol;

(f) 25 parts of the adduct of 4 moles of ethylene oxide to 1 mole ofm-n-dodecylphenol or p-n-dodecylphenol;

(g) 30 parts of the adduct of 6 moles of ethylene oxide to 1 mole ofp-isopentadecylphenol.

EXAMPLE 3 30 parts of finely divided dye C.I. No. 15,675 is dissolved in500 parts of water and then 20 parts of the sodium salt of the sulfuricacid hemiester of oleyl alcohol, 20 parts of the adduct of 4 moles ofethylene oxide to 1 mole of isononanol, 10 parts of p-chlorophenylmonoethylene glycol ether and 15 parts of glacial acetic acid are addedand the whole is made up to 1000 parts with water. Wool tops areimpregnated with this padding liquor, squeezed out and steamed forfifteen minutes at to 102 C. in an atmosphere of saturated steam.

A deep bluish red dyeing is obtained which is fast to rubbing and doesnot exhibit any streaks is obtained after washing.

Deep dyeings which are fast to rubbing are obtained in the same way byusing the following anion-active compounds instead of the sodium salt ofthe sulfuric acid hemiester of oleyl alcohol:

(a) 20 or 40 parts of the sodium salt of the sulfuric acid hemiester ofan adduct of 2 or 4 moles of ethylene oxide to 1 mole of nonylphenol;

(b) 20 parts of the sodium salt of an alkylsulfonic acid having fourteencarbon atoms;

(c) 20 parts of sodium monobenzylnaphthalene sulfonate;

(d) 25 or 50 parts of triethylammonium diisopropylnaphthalene sulfonate;

(e) 20 parts of the sodium salt of oleic tauride;

(f) 20 parts of the sodium salt of isohexylisopropylnaphthalene sulfonicacid.

EXAMPLE 4 20 parts of the finely divided dye C.I. No. 12,715 isdissolved in 500 parts of water and then 10 parts of triethanolammoniumn-decylbenzene sulfonate, 12 parts of the adduct of 4 moles of ethyleneoxide to 1 mole of isononanol,-5 parts of p-chlorophenyl monoethyleneglycol ether, 10 parts of the adduct of 40 moles of ethylene oxide to 1mole of castor oil and 5 parts of glacial acetic acid are added and thewhole is made up to 1000 parts with water.

Textured nylon-6 fibers, tufted onto a jute fabric, are impregnated withthe said solution, squeezed out with a. padding machine and steamed fortwenty minutes at 100 to 102 C. in an atmosphere of saturated steam.

After the fibers have been washed with water a deep bluish red nylontufted material is obtained, the jute component exhibiting only a slightdyeing.

In the same way:

(a) 20 parts of the dye C.I. No. 18,690 gives a reddish yellow dyeing;

(b) 20 parts of a dye obtained by mixing chroming of 1 mole of unchromeddye C.I. No. 12,715 and 1 mole of unchromed dye C.I. No. 12,174 gives ayellowish red dyeing; and

(c) 1 part of a dye obtained by mixed chroming of 1 mole of unchromeddye 0.1. No. 12,195 and 1 mole of 7 unchromed dye C.I. No. 12,197 givesa level pale grey dyeing.

EXAMPLE 20 parts of dye C.I. No. 61,135 is dissolved in 500 parts ofwater and then 20 parts of the triethanolamine salt ofn-decylbenzenesulfonic acid, 20 parts of the adduct of 6 moles ofethylene oxide to 1 mole of isodecanol, parts ofp-chlorophenylmonoethylene glycol ether and 10 parts of glacial aceticacid are added and the whole is made up to 1000 parts with water.

A wool tufted carpet which has not yet been coated 1s impregnated withthe said solution and squeezed out on a padding machine. It is thensteamed for twenty minutes at 100 to 102 C. with saturated steam andwashed with water. A greenish blue tufted material is obtained whichexhibits very good levelness and penetration of the dye.

Equally good results are obtained by replacing the pchlorophenylmonoethylene glycol ether by the following substances:

(a) 10 parts of o-chlorophenyl monoethylene glycol ether;

(b) parts of phenyl monoethylene glycol ether;

(c) parts of phenyldiethylene glycol ether;

(d) 15 parts of p-methylphenyl monoethylene glycol ether;

(e) 30 parts of fl-naphthyl diethylene glycol ether;

(f) 40 parts of the adduct of 1 mole of ethylene oxide to 1 mole of1,2-dihydroxybenzene; or

(g) 40 parts of the adduct of 2 moles of ethylene oxide to 1 mole of1,S-dihydroxynaphthalene.

We claim:

-1. A process for dyeing and printing fibers of natural or syntheticpolyamides by application of an aqueous solution which contains (a) atleast one anionic dye and (b), in 1000 parts by weight, 5 to 60 parts byweight of at least one anion-active dyeing assistant to the fibers at atemperature which is lower than the absorption temperature of all thedyes present, said anion-active dyeing assistant being a water-solublesalt of a sulfuric acid hemiester of an aliphatic alcohol having ten totwenty carbon atoms, of a sulfuric acid hemiester of an adduct of analkylphenol having six to twelve carbon atoms in the alkyl radical to a1 to 5 molar amount of ethylene oxide, of an alkyl or alkylaryl sulfonicacid with ten to twenty carbon atoms or of N-acyltaurines having 10 to20 carbon atoms in the acyl radical, and finishing off the dyeing orprint by steaming with or without treatment with a hot aqueous acidliquor, wherein the dye solution also contains in each each 1000 partsby weight: (c) 5 to 30 parts by weight of at least one adduct of 2 to 8moles of ethylene oxide to 1 mole of an aliphatic alcohol having six toeighteen carbon atoms or of 2 to 6 moles of ethylene oxide to 1 mole ofan alkylphenol having six to fifteen carbon atoms in the alkyl radical;and (d) 5 to 40 parts by weight of at least one monophenyl ether ormononaphthyl ether of ethylene glycol or diethylene glycol which maybear on the aromatic nucleus a halogen atom, a hydroxyl group, a phenylgroup, an alkyl group having up to five carbon atoms or an alkoxy grouphaving up to five carbon atoms.

2. A process as claimed in claim 1 in which components (b) and (c) areused in the weight ratio 0.25:1 to 2:1.

3. A process as claimed in claim 1 in which 2 to 4 parts by weight of anadduct of 10 to 80 moles of ethylene oxide to 1 mole of an aliphaticalcohol having ten to twenty carbon atoms, an alkylphenol having ten totwenty carbon atoms, a fatty acid having ten to twenty carbon atoms or aglyceride thereof or a reaction product thereof with an alkanolamine oran alkylamine having ten to twenty carbon atoms, is added to 1000 partsby weight of dye solution 4. A process as claimed in claim 1 whereinp-chloro phenyl ethylene glycol ether is used as component (d).

5. A process as claimed in claim 1 in which at least one adduct of 3 to6 moles of ethylene oxide to 1 mole of a branched alcohol having six tofifteen carbon atoms is used as component (c).

6. A process as claimed in claim 1 in which at least one adduct of 2 to4 moles of ethylene oxide to 1 mole of an alkylphenol having eight toten carbon atoms in the alkyl radical is used as component (0).

7. A process as claimed in claim 1 wherein a dye solution is used whichconsists of ingredients (a) through (d) in water.

8. An assistant mixture for carrying out the process of claim 1 andcomprising the following components: (i) 5 to parts by weight of atleast one anion-active dyeing assistant, said assistant being awater-soluble salt of a sulfuric acid hemiester of an aliphatic alcoholhaving ten to twenty carbon atoms, of a sulfuric acid hemiester of anadduct of an alkylphenol having six to twelve carbon atoms in the alkylradical to a l to 5 molar amount of ethylene oxide, of an alkyl oralkylaryl sulfonic acid with ten to twenty carbon atoms or ofN-acryltaurines having 10 to 20 carbon atoms in the acyl radical; (ii) 5to 30 parts by weight of at least one aduct of 2 to 8 moles of ethyleneoxide to 1 mole of an aliphatic alcohol having six to eighteen carbonatoms or of 2 to 6 moles of ethylene oxide to 1 mole of an alkylphenolhaving six to fifteen carbon atoms in the alkyl radical; and (iii) 5 to40 parts by weight of at least one monophenyl ether or mononaphthylether of ethylene glycol or diethylene glycol which may bear on thearomatic nucleus a halogen atom, a hydroxyl group, a phenyl group, analkyl group having up to five carbon atoms or an alkoxy group having upto five carbon atoms.

References Cited UNITED STATES PATENTS 3,334,960 8/1967 Abel. 3,363,972l/ 1968 Ulrich et al.

NORMAN G. TORCHIN, Primary Examiner.

J. E. CALLAGHAN, Assistant Examiner.

US. Cl. X.R. 893

1. A PROCESS FOR DYEING AND PRINTING FIBERS OF NATURAL OR SYNTHETIC POLYAMIDES BY APPLICATION OF AN AQUEOUS SOLUTION WHICH CONTAINS (A) AT LEAST ONE ANIONIC DYE AND (B), IN 1000 PARTS BY WEIGHT, 5 TO 60 PARTS BY WEIGHT OF AT LEAST ONE ANION-ACTIVE DYEING ASSISTANT TO THE FIBERS AT A TEMPERATURE WHICH IS LOWER THAN THE ABSORPTION TEMPERATURE OF ALL THE DYES PRESENT, SAID ANION-ACTIVE DYEING ASSISTANT BEING A WATER-SOLUBLE SALT OF A SULFURIC ACID HEMIESTER OF AN ALIPHATIC ALCOHOL HAVING TEN TO TWENTY CARBON ATOMS, OF A SULFURIC ACID HEMIESTER OF AN ADDUCT OF AN ALKYLPHENOL HAVING SIX TO TWELVE CARBON ATOMS IN THE ALKYL RADICAL TO A 1 TO 5 MOLAR AMOUNT OF ETHYLENE OXIDE, OF AN ALKYL OR ALKYLARYL SULFONIC ACID WITH TEN TO TWENTY CARBON ATOMS OR OF N-ACYLTAURINES HAVING 10 TO 20 CARBON ATOMS IN THE ACYL RADICAL, AND FINISHING OFF THE DYEING OR PRINT BY STEAMING WITH OR WITHOUT TREATMENT WITH A HOT AQUEOUS ACID LIQUOR, WHEREIN THE DYE SOLUTION ALSO CONTAINS IN EACH EACH 1000 PARTS BY WEIGHT: (C) 5 TO 30 PARTS BY WEIGHT OF AT LEAST ONE ADDUCT OF 2 TO 8 MOLES OF ETHYLENE OXIDE TO 1 MOLE OF AN ALIPHATIC ALCOHOL HAVING SIX TO EIGHTEEN CARBON ATOMS OR OF 2 TO 6 MOLES OF EHTYLENE OXIDE TO 1 MOLE OF AN ALKYLPHENOL HAVING SIX TO FIFTEEN CARBON ATOMS IN THE ALKYL RADICAL; AND (D) 5 TO 40 PARTS BY WEIGHT OF AT LEAST ONE MONOPHENYL ETHER OR MONONAPHTHYL ETHER OF ETHYLENE GLYCOL OR DIETHLENE GLYCOL WHICH MAY BEAR ON THE AROMATIC NUCLEUS A HALOGEN ATOM, A HYDROXYL GROUP, A PHENYL GROUP, AN ALKYL GROUP HAVING UP TO FIVE CARBON ATOMS OR AN ALKOXY GROUP HAVING UP TO FIVE CARBON ATOMS. 